Octahydroindole phosphorylacylamines

ABSTRACT

Phosphorylthio-acetyl derivatives of decahydroquinolines, octahydroindoles and octahydropyrindines are effective plant regulating agents (growth regulators and selective herbicides) and fungicides. 
     The new phosphorylacylamines correspond to the formula I ##SPC1## 
     wherein R 1  and R 2  each independently represents hydrogen or methyl, R 3  represents alkyl or haloalkyl, R 4  represents alkyl, alkoxy, haloalkoxy, alkylthio or an amino radical, X represents oxygen or sulphur, and one of the two indices m and n represents 1 and the other represents 0 or 1.

This is a division of application Ser. No. 324,469 filed on Jan. 17,1973, now U.S. Pat. No. 3,876,643.

The present invention relates to phosphoryl-acyl-amines, a process fortheir manufacture, also to agents which contain these new compounds asplant regulating and fungicidal active substances, as well as to amethod of combating weeds and phytopathogenic fungi and to a method ofregulating the growth of useful plants which comprises the use of thenew active substances or of agents which contain them.

The new phosphorylacylamines correspond to the formula I ##SPC2##

wherein R₁ and R₂ each independently represents hydrogen or methyl, R₃represents alkyl or haloalkyl, R₄ represents alkyl, alkoxy, haloalkoxy,alkylthio or an amino radical, X represents oxygen or sulphur, and oneof the two indices m and n represents 1 and the other represents 0 or 1.

By alkyl radicals R₃ and R₄ are meant straight-chain or branchedradicals with 1 to 4 carbon atoms, such as the methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec.- or tert. butyl radical. Such alkylradicals also for the alkyl moiety of haloalkyl radicals R₃ and ofalkoxy, haloalkoxy or alkylthio radicals R₄. Halogen as substituents ofan haloalkyl or haloalkoxy radical can be fluorine, chlorine, bromine oriodine, in particular chlorine or bromine.

The new phosphoric esters of the formula I are obtained according to thepresent invention by converting a heterocycle of the formula II ##SPC3##

with a halogenated acylating agent into compounds of the formula III##SPC4##

and subsequently reacting these either in the presence of an acidbinding agent with a phosphoric ester of the formula IV ##EQU1## or withan alkali salt or an ammonium salt of such a phosphoric ester.

In the formulae II to IV R₁, R₂, R₃, R₄, X, m and n have the meaningsgiven under the formula I, Hal in formula III represents a halogen atom,preferably chlorine or bromine.

The reactions are carried out in the presence of solvents or diluentswhich are inert towards the reactants. The following solvents ordiluents can be used for example: aliphatic, aromatic or halogenatedhydrocarbons, such as benzene, toluene, xylene, chlorobenzene, methylenechloride, chloroform; ethers and ethereal compounds, such as dialkylether, dioxan, tetrahydrofuran; ketones, such as acetone, methyl ethylketone; nitriles, such as acetonitrile; N,N-dialkylated amides, such asdimethyl formamide; also dimethyl sulphoxide, as well as mixtures ofthese solvents with one another.

As halogenated acylating agents there are used preferably halogenatedalkanecarboxylic acid halides, such as chloroacetyl chloride orα-chloropropionyl chloride. However, it is also possible to carry outthe reaction with halogenated alkanecarboxylic acid anhydrides, e.g.chloroacetic anhydride. When using halogenated alkanecarboxylic acidhalides the haloacylation is carried out in the presence of an acidbinding agent. Suitable acid binding agents are: tertiary amines, suchas trialkylamines, e.g. triethylamine, pyridine and pyridine bases, orinorganic bases, such as the oxides, hydroxides, hydrogen carbonates andcarbonates of alkali and alkaline earth metals. It is also possible touse as acid binding agent the respective reactant of the formula II,which in this case must be used in excess. The compounds of the formulaII obtained by these reactions have hitherto not been described.

The reaction temperatures are between 0° and 100°C, preferably between0° and 60°C.

The compounds encompassed by formula I can be in two isomeric forms,namely in the cis- and trans-configuration. The following connexionsapply:

a. octahydropyrindene is in the cis-form by virtue of its ringsynthesis. Accordingly, the compounds of the formula I derived therefromare also in the cis-form.

b. Octahydroindole derivatives of the formula I are mixtures of the cis-and trans-form.

c. Decahydroquinoline can be manufactured as pure cis- or trans-form.Accordingly, the compounds of the formula I derived therefrom are alsoin the cis- or trans-form. However, in practice the stereospecificdecahydroquinoline used as starting product will also contain a slightamount of the other isomer. But this does not as a rule impair theactivity spectrum of the desired isomer.

d. Decahydroquinaldine derivatives of the formula I are mixtures of thecis- and trans-form.

The followiing Example will serve to illustrate the process according tothe invention. In the accompanying Tables (a), (b) and (c) there aresummarised further compounds of the formula I which were obtained by theprocess described in the Example, or by one of the variants thereofmentioned hereinbefore; new intermediate products of the formula III arelisted in Table (d).

EXAMPLE

a. A solution of 20 g of trans-decahydroquinoline in 150 ml of diethylether is treated with a solution of 5.75 g of sodium hydroxide in 150 mlof water. While stirring vigorously, 16.3 g of chloroacetyl chloride areadded dropwise at 0°-10°C and the reaction mixture is further stirredfor 2 hours at room temperature. The organic phase is then isolated,washed neutral with water, dried, and the solvent evaporated in vacuo.The residual oil is distilled in a high vacuum to give 26 g of1-chloroacetyl-trans-decahydroquinoline as a colourless oil with aboiling point of 104-108°C/0.05 Torr.

b. To a solution of 11 g of 1-chloroacetyl-trans-decahydro-quinoline in100 ml of acetone is added a solution of 10 g of the potassium salt of0,0-dimethyldithiophosphoric acid in 100 ml of acetone and the mixtureis allowed to stand for 24 hours at 25°C. The precipitated potassiumchloride is filtered off and the solvent distilled in vacuo to leave asresidue 15 g of1-(0,0-dimethyl-thiophosphorylthio-acetyl)-trans-decahydroquinoline as ayellow oil; n_(D) ²⁰ = 1.5515. [Compound 45]. The following phosphoricesters encompassed by the formula I were obtained in the way describedin the preceding Example:

                  Table a                                                         ______________________________________                                        Octahydropyrindine derivatives                                                 ##STR1##                                                                     Comp. R.sub.1  R.sub.2 R.sub.3                                                                              R.sub.4 X   n.sub.D.sup.20                      No.                                                                           ______________________________________                                        1     H        H       CH.sub.3                                                                             OCH.sub.3                                                                             S   1.5502                              2     H        H       C.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                      S   1.5465                              3     H        H       C.sub.3 H.sub.7 (iso)                                                                OC.sub.3 H.sub.7 (iso)                                                                S   1.5340                              4     H        H       C.sub.3 H.sub.7 (n)                                                                  OC.sub.3 H.sub.7 (n)                                                                  S   1.5375                                                                        n.sub.D.sup.24 =                    5     H        CH.sub.3                                                                              C.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                      S   1.5366                                                                        n.sub.D.sup.24 =                    6     H        H       C.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                      O   1.5175                              7     H        H       C.sub.2 H.sub.5                                                                      SC.sub.3 H.sub.7 (n)                                                                  O   viscos                              8     H        H       CH.sub.3                                                                             OCH.sub.3                                                                             O   viscos                              9     H        CH.sub.3                                                                              C.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                      O   Oel                                 10    H        H       C.sub.2 H.sub.5                                                                      CH.sub.3                                                                              S   Oel                                 11    3-CH.sub.3                                                                             H       C.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                      S   1.5372                              12    3-CH.sub.3                                                                             H       C.sub.3 H.sub.7 (n)                                                                  OC.sub.3 H.sub.7 (n)                                                                  S   1.5318                              13    4-CH.sub.3                                                                             H       C.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                      S   1.5416                              14    4-CH.sub.3                                                                             H       C.sub.3 H.sub.7 (n)                                                                  OC.sub.3 H.sub.7 (n)                                                                  S   1.5354                              15    4-CH.sub.3                                                                             H       C.sub.3 H.sub.7 (iso)                                                                OC.sub.3 H.sub.7 (iso)                                                                S   1.5299                              ______________________________________                                    

                                      Table b                                     __________________________________________________________________________    Decahydroquinoline derivatives                                                 ##STR2##                                                                     Comp.                                                                             R.sub.1                                                                            R.sub.2                                                                          R.sub.3                                                                              R.sub.4                                                                              X configu-                                                                           n.sub.D.sup.20                               No.                         ration                                            __________________________________________________________________________    16  H    H  C.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                     S trans                                                                              1.5435                                       17  H    H  C.sub.3 H.sub.7 (iso)                                                                OC.sub.3 H.sub.7 (iso)                                                               S trans                                                                              1.5289                                       18  H    H  C.sub.3 H.sub.7 (n)                                                                  OC.sub.3 H.sub.7 (n)                                                                 S trans                                                                              1.5354                                                                        n.sub.D.sup.24 =                             19  H    H  C.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                     O trans                                                                              1.5685                                       20  H    H  CH.sub.2 CH.sub.2 Cl                                                                 OCH.sub.2 CH.sub.2 Cl                                                                O trans                                                                              oil                                          21  H    H  C.sub.2 H.sub.5                                                                      OC.sub.4 H.sub.9 (sec)                                                               O trans                                                                              oil                                          22  H    H  CH.sub.3                                                                             OCH.sub.3                                                                            S cis  1.5530                                       23  H    H  C.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                     S cis  1.5454                                       24  H    H  C.sub.3 H.sub. 7 (iso)                                                               OC.sub.3 H.sub.7 (iso)                                                               S cis  1.5332                                       25  H    H  C.sub.3 H.sub.7 (n)                                                                  OC.sub.3 H.sub.7 (n)                                                                 S cis  1.5300                                                                        n.sub.D.sup.24 =                             26  H    CH.sub.3                                                                         C.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                     S cis  1.5349                                       27  H    H  C.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                     O cis  n.sub.D.sup.24 =                                                              1.5175                                       28  H    H  C.sub.2 H.sub.5                                                                      SC.sub.3 H.sub.7 (n)                                                                 O cis  oil                                          29  H    H  C.sub.2 H.sub.5                                                                      NH.sub.2                                                                             O cis  viscous                                      30  H    H  CH.sub.3                                                                             OCH.sub.3                                                                            O trans                                                                              oil                                          31  H    H  CH.sub.3                                                                             OCH.sub.3                                                                            O cis  oil                                          32  H    H  CH.sub.3                                                                             OC.sub.4 H.sub.9 (n)                                                                 O cis  oil                                          33  2-CH.sub.3                                                                         H  C.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                     S cis/                                                                          trans                                                                              1.5436                                       34  2-CH.sub.3                                                                         H  C.sub.3 H.sub.7 (n)                                                                  OC.sub.3 H.sub.7 (n)                                                                 S cis/                                                                          trans                                                                              1.5339                                       35  2-CH.sub.3                                                                         H  C.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                     O cis/ oil                                                                      trans                                             __________________________________________________________________________

                  Table c                                                         ______________________________________                                        Octahydroindole derivatives                                                    ##STR3##                                                                     Comp. R.sub.1  R.sub.2                                                                             R.sub.3 R.sub.4   X   n.sub.D.sup.20                     No.                                                                           ______________________________________                                        36    H        H     C.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                        S   1.5458                             37    H        H     C.sub.3 H.sub.7 (n)                                                                   OC.sub.3 H.sub.7 (n)                                                                    S   1.5365                             38    H        H     C.sub.3 H.sub.7 (iso)                                                                 OC.sub.3 H.sub.7 (iso)                                                                  S   1.5318                             39    H        H     CH.sub.3                                                                              OCH.sub.3 O   oil                                40    2-CH.sub.3                                                                             H     CH.sub.3                                                                              OCH.sub.3 S   1.5483                             41    2-CH.sub.3                                                                             H     C.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                        S   1.5380                             42    2-CH.sub.3                                                                             H     C.sub.3 H.sub.7 (n)                                                                   OC.sub.3 H.sub.7 (n)                                                                    S   1.5368                             43    2-CH.sub.3                                                                             H     C.sub.3 H.sub.7 (iso)                                                                 OC.sub.3 H.sub.7 (iso)                                                                  S   1.5267                             44    2-CH.sub.3                                                                             H     C.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                        O   wax                                ______________________________________                                    

                  Table d                                                         ______________________________________                                        Intermediate products of the formula III                                      Compound              Physical Data                                           ______________________________________                                        1-chloroacetyl-cis-decahydroquinoline                                                               m.p.:    88°-90°C                         1-chloroacetyl-2-methyl-decahydro-                                                                  n.sub.D.sup.20 =                                                                       1,5175                                         quinoline                                                                     1-chloroacetyl-octahydro-1H-indole                                                                  b.p.:    112°-118°                                                       0,03 Torr                                      1-chloroacetyl-2-methyl-octahydro-                                                                  b.p.:    106°-110°                        1H-indole                      0,04 Torr                                      1-chloroacetyl-octahydro-1H-                                                                        b.p.:    104°-107°                        1-pyridine                     0,1 Torr                                       1-chloroacetyl-3-methyl-octahydro-                                                                  b.p.:    115°/                                   1H-1-pyrindine                 0,17 Torr                                      1-chloroacetyl-4-methyl-octahydro-                                                                  n.sub.D.sup.20 =                                                                       1,5180                                         1H-1-pyrindine                                                                1-α-chloropropionyl-cis-decahydro-                                                            n.sub.D.sup.20 =                                                                       1,5154                                         quinoline                                                                     1-α-chloropropionyl-octahydro-                                                                n.sub.D.sup.20 =                                                                       1,5165                                         1H-1-pyrindine                                                                ______________________________________                                    

The active substances according to the invention have very good plantregulating properties. As herbicides they have very good action againstPanicum type plants such as Setaria sp. and Digitaria sp. and againstgrasses, such as Lolium sp., Alopecurus sp. and Poa sp., without causingdamage to cultivated plants, for example such as soya beans, cotton,sugar beet, maize or cereals.

Furthermore, difficultly combattable weeds in rice cultures (cultures ofdry and water rice), such as Echinochloa sp., are attacked and destroyedby these active substances. Since the active substances are non-toxic inconventional rates of application and do not upset the balance ofnature, they are highly suitable for application in cultures of waterrice. However, they can also be used for the important task ofcombatting weeds in areas of land surrounding the rice cultures, such asditches, canal beds, embankments etc.

The active substances are applied before and after germination of theplants (pre- and postemergence).

The regulation of useful plants with the compounds of the formula Iprimarily takes the form of a uniform or partial growth inhibition.Cotton, soya or cereals flourish as plants of diminished size andreduced internodal intervals without any accompanying decrease in theharvest yield. The stability of the plants is improved and the tendencyto break (to lie flat) induced by high winds, thunderstorms, orhailstorms, is substantially reduced. The partial growth inhibition isto be understood both in the sense of time of growth and location in theplant.

It is possible to prevent the growth of undesirable shoots, e.g. intobacco plants or ornamental plants. A decrease in growth occurs ingrasses.

In addition, the compounds of the formula I also display effects whichimpinge directly on the process of improvement of the harvest yield.

Moreover, the compounds of the formula I possess excellent fugicidalproperties against phytopathogenic fungi. Fungus infections occuring onfruit, blossoms, leaves, stems and roots can be checked or destroyedwith the new active substances and parts of plants which grow laterremain protected from such infections. The new active substances haveextraordinarily good activity against Pirisularia species, such asPiricularia oryzae and mildew fungus species, such as Erysiphezucchetti.

On account of their good herbicidal and fungicidal properties interestattaches to phosphoric esters of the formula Ia ##SPC5##

wherein R₁, X, m and n have the meanings given under the formula I,R_(1') represents an alkyl radical with 1 to 3 carbon atoms and R_(4")represents an alkoxy radical with 1 to 3 carbon atoms.

The intermediate products of the formula III possess good herbicidalproperties.

The herbicidal action of the compounds according to the invention wasdetermined in the light of the following tests:

1. Herbicidal action on preemergence application

Immediately after the test plants have been sown, the active substancesare applied to the surface of the soil as an aqueous dispersion(obtained from a 25% wettable powder). The seed dishes are then kept at22°-25°C relative humidity. The test is evaluated after 28 days.

The test plants used were:

Cultivated plants:

soya beans (Glycine hyspida)

cotton (Gossypium herbaccara)

sugar beet (beta vulgaris)

Weeds:

Digitaria sanguinale

Setaria italica

Alopecurus myosuroides

Lolium multiflorum

Poa trivialis

The respective rates of application are to be found in the followingTable. Evaluation is according to the following rating:

9 = plants undamaged (control)

1 = plants destroyed

2-8 = intermediate stages of damage

            Rate of application                                                                      Digitaria                                                                           Setaria                                                                            Alopecurus                                                                           Lolium Poa                                       in         sanguinale                                                                          italica                                                                            myosuroides                                                                          multiflorum                                                                          trivalis                          Compound No.                                                                          kg/ha                                                                 __________________________________________________________________________    16      4          1     1    1      1      1                                         2          1     3    2      2      1                                         1          3     3    3      3      1                                 2       4          1     1    1      1                                                2          1     2    1      3                                                1          3     3    3      4                                        23      4          1     1    2      1                                                2          2     2    2      2                                                1          2     4    3      3                                        1       4          1     1           2      1                                         2          1     1           3      1                                         1          --    3           --     1                                 22      4          2     1                                                            2          2     1                                                            1          3     3                                                    __________________________________________________________________________

The cited cultivated plants, soya beans, cotton and sugar beet, as wellas cereals (wheat and oats), are neither damaged nor hindered in theirgrowth by the active substances listed hereinabove.

2. Preemergence test in rice in which weeds have been sown

a. Dry test

In pots filled with garden soil are sown as test plant rice (OryzaOryzoides) and as weed Echinochloa crus galli. The active substance isprocessed to a 25% wettable powder and is applied to the surface of thesoil in the form of an aqueous dispersion immediately after the sowing(amount of broth: 100 ml /m²).

b. Wet test

The aqueous dispersion of the active substance is applied to the surfaceof the test pots and worked in to a depth of about 1 cm. Then the testplants (rice and Echinochloa crus galli) are sown and the soil iscompletely saturated with water. Upon emergence of the seed, the waterlevel in the pots is brought to about 2-3 cm above the surface of thesoil.

Both tests are carried out in a greenhouse at 24°- 27°C and 70% relativehumidity. The evaluation is carried out 28 days later according to therating given in Test 1.

    __________________________________________________________________________            Rate of application                                                                      Dry test  Wet test                                         Compound No.                                                                          in kg/ha                                                                                 Echinochloa                                                                             Echinochloa                                                         crus galli                                                                           Rice                                                                             crus galli                                                                           Rice                                      __________________________________________________________________________    22      4          1      8  2      8                                                 2          1      8  2      8                                         16      4          1      9  2      8                                                 2          1      9  2      9                                         23      4          2      8  2      8                                                 2          2      8  2      8                                          1      4          2      8  --     --                                                2          2      9  --     --                                        __________________________________________________________________________

3. Inhibition of side-shoot formation in tobacco

Tobacco plants of the variety "Sota 27" were cultivated in the open inaccordance with practice. One month before harvesting (22nd. August) theinflorescences were pruned. All the plants were then sprayed drippingwet with a specific active substance concentration for each 5 m² area.During the harvesting on 20th. September, the weight of side-shoots ofall plants determined per plot was assessed in proportion to the numberof plants. The average weight of side-shoots per plant was ascertainedtherefrom. In the same way the average number of side-shoots per plantwas determined. The following results were obtained:Compound No. Rate ofappli- Weight of Number of cation of side-shoots side-shoots activeSubst- per plant per plant ance______________________________________2510 kg/ha 30 g 1,7 5 kg/ha 70 g 4,9 4 10 kg/ha 55 g 2,5 5 kg/ha 55 g2,4untreated -- 225 g 7,0control______________________________________

4. Inhibition of growth in length in cereals

Very thickly sown summer barley of the variety "Union" was sprayed withan active substance solution at the end of the tillering period on 10th.May. A plot having an area of 3 m² was allotted to each active substanceconcentration. Evaluation took place on 17th. July shortly beforeharvesting and comprised the height of the plants and the degree towhich they lay flat induced by the density of sowing (= stalks lyingflat).

    ______________________________________                                        Compound No.                                                                            Rate of appli-                                                                             Height of the                                                                            Degree to                                             cation of    plants     which plants                                          active Substance                                                                           (average)  lie flat                                    ______________________________________                                        25        4 kg/ha       85 cm     -                                                     2 kg/ha      105 cm     +                                            4        4 kg/ha       75 cm     -                                                     2 kg/ha      100 cm     -                                           control   --           115 cm      + +                                        ______________________________________                                         Explanation:                                                                  + + = lying very flat                                                          + = lying flat                                                                - = plants standing upright                                             

The fungicidal action of the compounds according to the invention wasdetermined by the following test:

Action against Piricularia oryzae

Rice plants are cultivated in a greenhouse and in the 1-2 leaf stage aresprayed with an aqueous spray broth which contains 0.05% of therespective active substance. Two days later the plants are infected withan aqueous conidia suspension of Piricularia oryzae and incubated in ahumid chamber at 27°C. The test is evaluated after 6 days.

The plants treated with compounds

no.'s 2,14 -- Table (a)

no. 17 -- Table (b)

no.'s 38,41,42 -- Table (c)

showed no attack by fungus, whereas the untreated plants were 100%attacked.

The agents according to the invention are manufactured in known mannerby intimately mixing and/or grinding active substances of the formula Iwith the suitable carriers, optionally with the addition of dispersantsor solvents which are inert towards the active substances. The activesubstances may take and be used in the following forms:

Solid forms:

dusts, tracking agents, granules, coated granules, impregnated granulesand homogeneous granules.

Liquid forms:

a. active substances which are dispersible in water: wettable powders,pastes, emulsions;

b. solutions.

To manufacture solide forms ) dusts, tracking agents), the activesubstances are mixed with solid carriers. Suitable carriers are, forexample: kaolin, talcum, bolus, loess, chalk, limestone, groundlimestone, attaclay, dolomite, diatomaceous earth, precipitated silica,alkaline earth silicates, sodium and potassium aluminium silicates(feldspar and mica), calcium and magnesium sulphates, magnesium oxide,ground synthetic materials, fertilisers, for example ammonium sulphate,ammonium phosphate, ammonium nitrate, urea, ground vegetable products,such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder,residues of plant extractions, activated charcoal etc. These substancescan either be used singly or in admixture with one another.

The particle size of the carriers for dusts is advantageously up to 0.1mm, for tracking agents from about 0.075 to 0.2 mm, and for granules 0.2mm or larger.

The solid forms contain the active substances in concentrations from 0.5to 80%.

To these mixtures can also be added additives which stabilize the activesubstance and/or non-ionic, anionic and cationic surface activesubstances, which for example improve the adhesion of the activeingredients on plants or parts of plants (adhesives and agglutinants)and/or ensure a better wettability (wetting agents) and dispersibility(dispersing agents). Examples of suitable adhesives are the following:olein/chalk mixture, cellulose derivatives (methyl cellulose,carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl anddialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and8 to 9 carbon atoms in the alkyl radical, lignin sulphonic acids, theiralkali metal and alkaline earth metal salts, polyethylene glycol ethers(carbowaxes), fatty alcohol polyethylene glycol ethers having 5 to 20ethylene oxide radicals per molecule and 8 to 18 carbon atoms in thefatty alcohol moiety, condensation products of urea and formaldehyde,and also latex products. Preferred dispersions (suspensions andemulsions) are manufactured by mixing or grinding the active substancewith carriers accompanied by the addition of dispersing agents andsolvents, in the process of which there result firstly dispersibleactive substance concentrations, such as wettable powders andemulsifiable concentrates.

The water-dispersible concentrates of the active substance i.e. wettablepowders, pastes and emulsifiable concentrates are agents which can bediluted with water to any concentration desired. They consist of activesubstance, carrier, optionally additives which stabilize the activesubstance, surface-active substances and anti-foam agents and,optionally, solvents. The active substance concentrations in theseagents are from 5-80%.

Wettable powders and pastes are obtained by mixing and grinding theactive substances with dispersing agents and pulverulent carriers insuitable apparatus until homogeneity is attained. Carriers are, forexample, those mentioned for the solid forms of application. In somecases it is advantageous to use mixtures of different carriers. Asdispersing agents there can be used, for example, condensation productsof sulphonated naphthalene and sulphonated naphthalene derivatives withformaldehyde, condensation products of naphthalene or naphthalenesulphonic acids with phenol and formaldehyde, as well as alkali,ammonium and alkaline earth metal salts of lignin sulphonic acid, inaddition, alkylaryl suphonates, alkali and alkaline earth metal salts ofdibutyl naphthalene sulphonic acid, fatty alcohol sulphates such assalts of sulphated hexadecanols, heptadecanols, octadecanols, and saltsof sulphated fatty alcohol glycol ethers, the sodium salt of oleoylethionate, the sodium salt of olcoyl methyl tauride, ditertiaryacetalene glycols, dialkyl dilauryl ammonium chloride and fatty acidalkali and alkaline earth metal salts.

Suitable anti-foam agents are silicones.

The active substance is so mixed, ground sieved and strained with theadditives mentioned above that, in wettable powders, the solid particlesize of from 0.02 to 0.04 and in pastes, of 0.03 is not exceeded. Toproduce emulsifiable concentrates and pastes, dispersing agents such asthose given in the previous paragraphs, organic solvents and water areused. Examples of suitable solvents are the following: alcohols,benzene, xylenes, toluene, dimethyl sulphoxide, and mineral oilfractions boiling between 120° and 350°C. The solvents must bepractically odorless, not phytotoxic, inert to the active substances andnot readily inflammable.

Furthermore, the agents according to the invention can be applied in theform of solutions. For this purpose the active substances or severalactive substances of general formula II are dissolved in suitableorganic solvents, mixtures of solvents or in water. Aliphatic andaromatic hydrocarbons, chlorinated derivatives thereof, slkylnaphthalenes and mineral oils singly or in admixture, can be used asorganic solvents. The solutions contain the active substance in aconcentration range from 1 to 20%.

In addition to fungicidal active substances, the agents describedaccording to the invention can be mixed with other biocidally activesubstances or agents. Thus in order to broaden the activity spectrum thenew agents may contain, for example, insecticides, fungicides,bactericides, fungistatics, bacteriostatics or nematocides, in additionto the cited active substance of the formula I. The agents according tothe invention may also contain plant fertilisers, trace elements etc.

The active substances of formula I can, for example, be formulated asfollows. The parts denote parts by weight.

Granules

The following substances are used to manufacture 5% granules:

5 parts of Compound No. 22, Table b),

0.25 parts of epichlorohydrin,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol ether,

91 parts of kaolin (particle size: 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and the mixturedissolved in 6 parts of acetone, then polyethylene glycol ether andcetyl polyglycol ether are added. The resulting solution is sprayed onkaolin and then evaporated in vacuo.

Wettable Powder

The following constituents are used to manufacture (a) a 50%, (b) a 25%and (c) a 10% wettable powder:

a. 50 parts of Compound No. 16, Table (b),

5 parts of sodium dibutylnaphthalene sulphonate,

3 parts of naphthalenesulphonic acid/phenolsulphonic acid/formaldehydecondensate (3:2:1),

20 parts of kaolin,

22 parts of Champagne chalk;

b. 25 parts of Compound No. 23, Table (b),

5 parts of oleylmethyltaurid-sodium-salt,

2.5 parts of naphthalenesulphonic acid/formaldehyde condensate,

0.5 part of carboxymethyl cellulose,

5 parts of neutral potassium-aluminium-silicate,

62 parts of kaolin;

c. 10 parts of Compound No. 41, Table (c),

3 parts of a mixture of the sodium salts of saturated fatty alcoholsulphates,

5 parts of naphthalenesulphonic acid/formaldehyde condensate,

82 parts of kaolin.

The indicated active substance is applied to the corresponding carriers(kaolin and chalk) and then these are mixed and ground, to yieldwettable powders of excellent wettability and having an excellentcapacity for forming suspensions. By diluting these wettable powderswith water it is possible to obtain suspensions of every desiredconcentration of active substance.

Paste

The following substances are used to manufacture a 45% paste:

45 parts of Compound No. 17, Table b),

5 parts of sodium aluminium silicate,

14 parts of cetyl polyglycol ether with 8 mols of ethylene oxide,

1 part of oleyl polyglycol ether with 5 mols of ethylene oxide,

2 parts of spindle oil,

10 parts of polyethylene glycol,

23 parts of water.

The active substance is intimately mixed with the addition inappropriate devices and ground. A paste is obtained from which, bydiluting it with water, is possible to manufacture suspensions of everydesired concentration of active substance. The suspensions are suitablefor treating vegetable plantations.

Emulsion Concentrate

To manufacture a 25% emulsion concentrate

25 parts of Compound No. 2, Table (a),

5 parts of a mixture of nonylphenolpolyoxy-ethoxy-ethylene and calcium,dodecylenesulphonate,

35 parts of 3,5,5-trimethyl-2-cyclohexan-1 -one,

35 parts of dimethyl formamide,

are mixed together. This concentrate can be diluted with water to giveemulsions in desired concentrations.

We claim:
 1. A phosphorylacylamine compound of the formula##SPC6##wherein R₁ is hydrogen or methyl, R₃ is alkyl of from 1 to 4carbon atoms, R₄ is alkoxy of from 1 to 4 carbon atoms, and X is oxygenor sulphur.
 2. A phosphorylacylamine according to Claim 1 in which R₃ isalkyl of from 1 to 3 carbon atoms and R₄ is alkoxy of from 1 to 3 carbonatoms. 3.1-O,O-diisopropyl-thiophosphorylthio-acetyl)-octahydro-1H-indoleaccording to claim 2 of the formula ##SPC7## 4.1-(O,O-diethyl-thiophosphorylthio)-2-methyl-octahydro-1H-indoleaccording to claim 2 of the formula ##SPC8## 5.1-(O,O-di-n-propyl-thisphosphorylthio-acetyl)-2-methyl-octahydro-IH-indoleaccording to claim 2 of the formula ##SPC9##